CN110482584A - A method of spherical calcium carbonate is prepared with egg shell - Google Patents
A method of spherical calcium carbonate is prepared with egg shell Download PDFInfo
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- CN110482584A CN110482584A CN201810453830.8A CN201810453830A CN110482584A CN 110482584 A CN110482584 A CN 110482584A CN 201810453830 A CN201810453830 A CN 201810453830A CN 110482584 A CN110482584 A CN 110482584A
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- calcium carbonate
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/18—Carbonates
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/18—Carbonates
- C01F11/185—After-treatment, e.g. grinding, purification, conversion of crystal morphology
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
Abstract
The present invention provides a kind of methods for preparing spherical calcium carbonate with egg shell, use egg shell for raw material, soluble calcium salt, which is made, with the calcium carbonate in appropriate acid solution dissolution egg shell can be prepared by spherical calcium carbonate using double decomposition using the protein in solution as chemical additives.Present invention process is simple, reaction process is easy to control, raw material is cheap and easy to get, and the protein directlyed adopt in egg shell substantially reduces production cost without in addition providing chemical additives as chemical additives；Acidolysis generates a small amount of polypeptide and free amino acid to partially protein in acid condition simultaneously, can effectively improve the efficiency of chemical additives, prepares the higher spherical calcium carbonate of purity；Also have many advantages, such as that small particle, uniform particle sizes, good dispersion, viscosity are smaller using spherical calcium carbonate prepared by method provided by the invention, can be used for the high-end purposes such as pharmaceutical carrier, inorganic template.
Description
Technical field
The invention belongs to technical field of inorganic nonmetallic materials more particularly to a kind of spherical calcium carbonate is prepared with egg shell
Method.
Background technique
Calcium carbonate is a kind of important industrial mineral raw material, can be divided into spindle, cube, aciculiform, ball according to form
Shape, chain lock shape, piece shape, amorphous etc..The calcium carbonate of different shape, application field and function are also different.It is wherein spherical
Calcium carbonate has the characteristics such as good mobility, dispersibility, wearability, is widely used in rubber, papermaking, coating, medicine, makeup
The various fields such as product.
Spherical calcium carbonate needs manually to prepare in nature without naturally occurring.And preparing ball calcium carbonate need to react
It is added suitable chemical additives in the process, existing chemical additives are mostly amino acid or protein of single high-purity etc.,
The higher cost of chemical additives.Also, that there are purity is lower, viscous for many lower spherical calcium carbonates generated of chemical additives regulation
Degree is big, bad dispersibility, the problems such as average particle size is larger and granularity is inhomogenous, and reaction process also tends to be difficult to control.Cause
It is an important research direction in industry that this, which seeks chemical additives that are a kind of economic and practical and regulating and controlling product excellent,.
Summary of the invention
In order to solve the above technical problem, the present invention provides a kind of methods for preparing spherical calcium carbonate with egg shell, comprising:
S1. egg husk as raw material is dissolved to obtain egg shell acid hydrolysis solution using acid solution；
S2. carbonate reagent is added into egg shell acid hydrolysis solution, using the protein in egg shell as chemical additives,
Calcium carbonate serosity is made using metathesis reaction；
S3. spherical calcium carbonate will be can be prepared by after calcium carbonate serosity drying.
It uses egg shell for raw material, and egg shell is dissolved using appropriate acid solution, it can after the proteolytic in egg shell
With directly as chemical additives, while partially protein acidolysis generates under acidic environment a small amount of polypeptide and free amino acid
The efficiency of chemical additives can be effectively improved, to generate the higher spherical calcium carbonate of purity.
Further, the egg husk as raw material is egg shell powder, and the preparation method of the egg shell powder includes: collection egg
Shell；Remaining egg liquid on egg shell is washed away with clear water；Dry 5h~8h, crushing can be obtained at 50 DEG C~100 DEG C after cleaning
Egg shell powder.
Further, the acid solution is by any one or in which several preparations in hydrochloric acid, citric acid, lactic acid, acetic acid
It forms.
Further, the concentration of the acid solution is 3mol/L~10mol/L.Acid solution selects above-mentioned concentration range can be with
Make polypeptide and free amino acid that suitable species are generated after protein acidolysis, for improving the efficiency of chemical additives, in favor of
Prepare the higher spherical calcium carbonate of purity
Further, the pH value of the egg shell acid hydrolysis solution is 1~3.5.In above-mentioned pH range, egg shell acid hydrolysis solution
The dissolubility that inside can be used for improving the amino acid of the efficiency of chemical additives is preferable.
Further, the step S2 is specifically included: it is 0.5mol/ that egg shell acid hydrolysis solution, which is first diluted to calcium ion concentration,
L~3mol/L；The sodium carbonate liquor that mass fraction is 15% is added into the solution after dilution again, in 25 DEG C~40 DEG C, stirring
10min~1h is reacted under conditions of rate 400rpm~700rpm can be obtained calcium carbonate serosity.Diluting egg shell acid hydrolysis solution can
Using deionized water, the calcium ion concentration after dilution will affect the partial size and content of the spherical calcium carbonate ultimately generated；If calcium
Ion concentration is too low, spherical calcium carbonate partial size can content bigger than normal or spherical calcium carbonate can be lower；If calcium ion concentration mistake
Although the partial size of height, spherical calcium carbonate reduces, but the content of spherical calcium carbonate also will be greatly reduced.
Further, the molar ratio of the calcium ion in the solution after the dilution and sodium carbonate is 1:1.
Further, the step S3 is specifically included: by calcium carbonate serosity with the revolving speed of 2000~3000rpm centrifugation 3~
5min, the sediment for being centrifuged acquisition are dried in vacuo 6 hours at 40 DEG C, can be prepared by spherical calcium carbonate.
Further, the particle size range of the spherical calcium carbonate is 0.8 μm~5 μm.
Compared with prior art, the beneficial effects of the present invention are:
The present invention uses egg shell to prepare spherical calcium carbonate for raw material, using the carbonic acid in appropriate acid solution dissolution egg shell
Soluble calcium salt is made in calcium, using the protein in solution as chemical additives, can be prepared by spherical carbonic acid using double decomposition
Calcium.Present invention process is simple, reaction process is easy to control, raw material is cheap and easy to get, directlys adopt the protein in egg shell as brilliant
Type controlling agent substantially reduces production cost without in addition providing chemical additives；Partially protein is sour in acid condition simultaneously
Solution generates a small amount of polypeptide and free amino acid, can effectively improve the efficiency of chemical additives, prepares the higher spherical shape of purity
Calcium carbonate；Also there is small particle using spherical calcium carbonate prepared by method provided by the invention, uniform particle sizes, good dispersion, glue
The advantages that smaller is spent, can be used for the high-end purposes such as pharmaceutical carrier, inorganic template.
Detailed description of the invention
Fig. 1 is 4.3k times of stereoscan photograph of the spherical calcium carbonate of the method preparation provided using the embodiment of the present invention 1；
Fig. 2 is 4.3k times of stereoscan photograph of the spherical calcium carbonate of the method preparation provided using the embodiment of the present invention 2；
Fig. 3 is 4.3k times of stereoscan photograph of the spherical calcium carbonate of the method preparation provided using the embodiment of the present invention 3；
Fig. 4 is 4.3k times of stereoscan photograph of the spherical calcium carbonate of the method preparation provided using the embodiment of the present invention 4.
Specific embodiment
Embodiment 1
A method of spherical calcium carbonate is prepared with egg shell, comprising:
S1. egg shell is collected, washes away remaining egg liquid on egg shell with clear water, is crushed after dry 5h at 50 DEG C after cleaning
Obtain egg shell powder；It takes appropriate egg shell powder sufficiently to be dissolved with the citric acid solution of 3mol/L, egg shell acid is then obtained by filtration
Liquid is solved, the pH value of control egg acid hydrolysis solution is 3.5；The content of calcium ion in egg shell acid hydrolysis solution is determined using EDTA titration；
S2. egg shell acid hydrolysis solution is diluted to calcium ion concentration is 3mol/L, and quality point is added into the solution after dilution
The sodium carbonate liquor that number is 15%, until the molar ratio of calcium ion and sodium carbonate is 1:1；In 25 DEG C, stirring rate 400rpm
Under the conditions of reaction 1h obtain calcium carbonate serosity；
S3. calcium carbonate serosity is centrifuged 5min with the revolving speed of 3000rpm, the sediment being centrifuged vacuum at 40 DEG C is dry
Dry 6 hours, spherical calcium carbonate is made.
The spherical calcium carbonate for the method preparation that embodiment 1 is provided is using electron-microscope scanning, 4.3k times of stereoscan photograph
As shown in Fig. 1.The form overwhelming majority of calcium carbonate in stereoscan photograph it can be seen from attached drawing 1 is spherical shape, spherical carbon
The purity of sour calcium can achieve 80% or so, therefore very using the purity of the spherical calcium carbonate of the method preparation of the offer of embodiment 1
It is high；Simultaneously as can be seen that the particle size range of spherical calcium carbonate is 0.8 μm~5 μm, particle size distribution range is simultaneously little, whole partial size
More uniformly；Spherical calcium carbonate particle does not occur obvious agglomeration, favorable dispersibility, and viscosity is lower.
Embodiment 2
A method of spherical calcium carbonate is prepared with egg shell, comprising:
S1. egg shell is collected, washes away remaining egg liquid on egg shell with clear water, is crushed after dry 8h at 60 DEG C after cleaning
Obtain egg shell powder；It takes appropriate egg shell powder sufficiently to be dissolved with the hydrochloric acid solution of 10mol/L, egg shell acidolysis is then obtained by filtration
Liquid, the pH value of control egg acid hydrolysis solution are 1；The content of calcium ion in egg shell acid hydrolysis solution is determined using EDTA titration；
S2. egg shell acid hydrolysis solution is diluted to calcium ion concentration is 0.75mol/L, and quality is added into the solution after dilution
The sodium carbonate liquor that score is 15%, until the molar ratio of calcium ion and sodium carbonate is 1:1；In 40 DEG C, stirring rate 500rpm
Under conditions of reaction 20min obtain calcium carbonate serosity；
S3. calcium carbonate serosity is centrifuged 3min with the revolving speed of 2000rpm, the sediment being centrifuged vacuum at 40 DEG C is dry
Dry 6 hours, spherical calcium carbonate is made.
The spherical calcium carbonate for the method preparation that embodiment 2 is provided is using electron-microscope scanning, 4.3k times of stereoscan photograph
As shown in Fig. 2.The form overwhelming majority of calcium carbonate in stereoscan photograph it can be seen from attached drawing 2 is spherical shape, spherical carbon
The purity of sour calcium can achieve 80% or so, therefore very using the purity of the spherical calcium carbonate of the method preparation of the offer of embodiment 2
It is high；Simultaneously as can be seen that the particle size distribution range of spherical calcium carbonate is very narrow, between 0.8 μm~2 μm, whole particle size is very
Uniformly；Spherical calcium carbonate particle does not occur obvious agglomeration, favorable dispersibility, and viscosity is lower.
Embodiment 3
A method of spherical calcium carbonate is prepared with egg shell, comprising:
S1. egg shell is collected, washes away remaining egg liquid on egg shell with clear water, dries powder after 7h after cleaning at 100 DEG C
Broken acquisition egg shell powder；It takes appropriate egg shell powder sufficiently to be dissolved with the lactic acid solution of 8mol/L, egg shell acid is then obtained by filtration
Liquid is solved, the pH value of control egg acid hydrolysis solution is 3；The content of calcium ion in egg shell acid hydrolysis solution is determined using EDTA titration；
S2. egg shell acid hydrolysis solution is diluted to calcium ion concentration is 1.5mol/L, and quality is added into the solution after dilution
The sodium carbonate liquor that score is 15%, until the molar ratio of calcium ion and sodium carbonate is 1:1；In 30 DEG C, stirring rate 700rpm
Under conditions of reaction 10min obtain calcium carbonate serosity；
S3. calcium carbonate serosity is centrifuged 4min with the revolving speed of 2500rpm, the sediment being centrifuged vacuum at 40 DEG C is dry
Dry 6 hours, spherical calcium carbonate is made.
The spherical calcium carbonate for the method preparation that embodiment 3 is provided is using electron-microscope scanning, 4.3k times of stereoscan photograph
As shown in Fig. 3.The form overwhelming majority of calcium carbonate in stereoscan photograph it can be seen from attached drawing 3 is spherical shape, spherical carbon
The purity of sour calcium can achieve 80% or so, therefore very using the purity of the spherical calcium carbonate of the method preparation of the offer of embodiment 3
It is high；Simultaneously as can be seen that the particle size range of spherical calcium carbonate is 0.8 μm~5 μm, particle size distribution range is simultaneously little, whole partial size
More uniformly；Spherical calcium carbonate particle does not occur obvious agglomeration, favorable dispersibility, and viscosity is lower.
Embodiment 4
A method of spherical calcium carbonate is prepared with egg shell, comprising:
S1. egg shell is collected, washes away remaining egg liquid on egg shell with clear water, is crushed after dry 8h at 60 DEG C after cleaning
Obtain egg shell powder；It takes appropriate egg shell powder sufficiently to be dissolved with the acetic acid solution of 6mol/L, egg shell acidolysis is then obtained by filtration
Liquid, the pH value of control egg acid hydrolysis solution are 3；The content of calcium ion in egg shell acid hydrolysis solution is determined using EDTA titration；
S2. egg shell acid hydrolysis solution is diluted to calcium ion concentration is 0.5mol/L, and quality is added into the solution after dilution
The sodium carbonate liquor that score is 15%, until the molar ratio of calcium ion and sodium carbonate is 1:1；In 35 DEG C, stirring rate 500rpm
Under conditions of reaction 30min obtain calcium carbonate serosity；
S3. calcium carbonate serosity is centrifuged 3min with the revolving speed of 2000rpm, the sediment being centrifuged vacuum at 40 DEG C is dry
Dry 6 hours, spherical calcium carbonate is made.
The spherical calcium carbonate for the method preparation that embodiment 4 is provided is using electron-microscope scanning, 4.3k times of stereoscan photograph
As shown in Fig. 4.The form overwhelming majority of calcium carbonate in stereoscan photograph it can be seen from attached drawing 4 is spherical shape, spherical carbon
The purity of sour calcium can achieve 80% or so, therefore very using the purity of the spherical calcium carbonate of the method preparation of the offer of embodiment 4
It is high；Simultaneously as can be seen that the particle size range of spherical calcium carbonate is 0.8 μm~5 μm, particle size distribution range is simultaneously little, whole partial size
More uniformly；Spherical calcium carbonate particle does not occur obvious agglomeration, favorable dispersibility, and viscosity is lower.
Finally it should be noted that the above examples are only used to illustrate the technical scheme of the present invention and are not limiting, although reference
Preferred embodiment describes the invention in detail, those skilled in the art should understand that, it can be to of the invention
Technical solution is modified or replaced equivalently, and without departing from the spirit and scope of the technical solution of the present invention, should all be covered
In scope of the presently claimed invention.
Claims (9)
1. a kind of method for preparing spherical calcium carbonate with egg shell, which is characterized in that the described method includes:
S1. egg husk as raw material is dissolved to obtain egg shell acid hydrolysis solution using acid solution；
S2. carbonate reagent is added into egg shell acid hydrolysis solution, using the protein in egg shell as chemical additives, uses
Calcium carbonate serosity is made in metathesis reaction；
S3. spherical calcium carbonate will be can be prepared by after calcium carbonate serosity drying.
2. the method according to claim 1, wherein the egg husk as raw material is egg shell powder, the egg shell
The preparation method of powder includes: collection egg shell；Remaining egg liquid on egg shell is washed away with clear water；At 50 DEG C~100 DEG C after cleaning
Lower dry 5h~8h, crushing can be obtained egg shell powder.
3. the method according to claim 1, wherein the acid solution is by hydrochloric acid, citric acid, lactic acid, acetic acid
Any one or in which several be prepared.
4. according to the method described in claim 3, it is characterized in that, the concentration of the acid solution is 3mol/L~10mol/L.
5. according to the method described in claim 4, it is characterized in that, the pH value of the egg shell acid hydrolysis solution is 1~3.5.
6. -5 any method according to claim 1, which is characterized in that the step S2 is specifically included: first by egg shell
It is 0.5mol/L~3mol/L that acid hydrolysis solution, which is diluted to calcium ion concentration,；It is 15% that mass fraction is added into the solution after dilution again
Sodium carbonate liquor, under conditions of 25 DEG C~40 DEG C, stirring rate 400rpm~700rpm react 10min~1h can be obtained
Calcium carbonate serosity.
7. according to the method described in claim 6, it is characterized in that, calcium ion and sodium carbonate in solution after the dilution
Molar ratio is 1:1.
8. according to the method described in claim 6, it is characterized in that, the step S3 is specifically included: by calcium carbonate serosity with
The revolving speed of 2000~3000rpm is centrifuged 3~5min, and the sediment for being centrifuged acquisition is dried in vacuo 6 hours at 40 DEG C, can be prepared by
Spherical calcium carbonate.
9. according to the method described in claim 8, it is characterized in that, the particle size range of the spherical calcium carbonate is 0.8 μm~5 μ
m。
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111921486A (en) * | 2020-07-09 | 2020-11-13 | 内江师范学院 | Nano calcium carbonate and preparation method and application thereof |
| CN115215363A (en) * | 2022-05-25 | 2022-10-21 | 华中农业大学 | Method for efficiently preparing eggshell source fine calcium carbonate and application thereof |
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| CN101045545A (en) * | 2007-04-17 | 2007-10-03 | 韶关学院 | Technology for producing light calcium carbonate using eggshell |
| CN101554387A (en) * | 2009-05-15 | 2009-10-14 | 于建泉 | Biological calcium carbonate extracting solution and production method thereof |
| US20140044620A1 (en) * | 2011-03-25 | 2014-02-13 | Essentron. Co., Ltd. | Method for producing precipitated calcium carbonate using fowl egg shells |
| CN104445333A (en) * | 2014-11-06 | 2015-03-25 | 安徽瑞研新材料技术研究院有限公司 | Process for producing calcium carbonate employing nano-precipitation method |
| JPWO2014061689A1 (en) * | 2012-10-17 | 2016-09-05 | 堺化学工業株式会社 | Surface-treated spherical calcium carbonate particles for cosmetics and method for producing the same |
| CN107473254A (en) * | 2017-10-12 | 2017-12-15 | 广西碳酸钙产业化工程院有限公司 | A kind of preparation method of spherical calcium carbonate |
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Patent Citations (6)
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|---|---|---|---|---|
| CN101045545A (en) * | 2007-04-17 | 2007-10-03 | 韶关学院 | Technology for producing light calcium carbonate using eggshell |
| CN101554387A (en) * | 2009-05-15 | 2009-10-14 | 于建泉 | Biological calcium carbonate extracting solution and production method thereof |
| US20140044620A1 (en) * | 2011-03-25 | 2014-02-13 | Essentron. Co., Ltd. | Method for producing precipitated calcium carbonate using fowl egg shells |
| JPWO2014061689A1 (en) * | 2012-10-17 | 2016-09-05 | 堺化学工業株式会社 | Surface-treated spherical calcium carbonate particles for cosmetics and method for producing the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111921486A (en) * | 2020-07-09 | 2020-11-13 | 内江师范学院 | Nano calcium carbonate and preparation method and application thereof |
| CN115215363A (en) * | 2022-05-25 | 2022-10-21 | 华中农业大学 | Method for efficiently preparing eggshell source fine calcium carbonate and application thereof |
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